Fluoro-acetyl ureas



United States Patent Ofiice 3&3457 Federated Wiley l8, 19$? 3,l.84,5tl7FLUQRfl-ACETYL UREA Otto Scherer, Frankfurt am Main, and GiinterSchneider,

Buchschlag, Germany, assignors to Farhwerlie Hoechst Aktiengesellsehaftvormals l /ieister Lucius dz Briining, Frankfurt am Main, Germany, acorporation of German No rowing. Filed ll liay 16, 1961, Ser. No.119,347 Claims priority, application Germany, May 28, 1969,

19 Claims. (Cl. 269-553) The invention relates to fluoro-acetyl ureasand their application as insecticides.

We have found that fiuoro-acetyl ureas of the general formula FCH-CONHCGNHR wherein R means an aliphatic, cycloal-i hatic, araliphatic oraromatic radical or the radical of an organic acid, can be prepared byreacting a monofluoro-acetyl halide with ureas of the general formulawherein R has the meaning given above, or by reactingmonofluoro-acctam-ide with isocyanates of the general formula wherein Rhas the meaning given above, or with com pounds which under the reactionconditions form isocyanates.

We have likewise found that N-monolluoro-acetyl-N'-monofiuoro-acetamidomethyl urea and N,N'bis-(monofiuoro-acetyD-urea canbe prepared by reacting monofluoro-acetamide with bromine in sodiumhydroxide solution and with oXal'yl chloride respectively.

Furthermore, the invention relates to the use of fluoroacetyl ureas ofthe general formula wherein R means hydrogen, an aliphatic,cycloaliphatic, araliphatic or aromatic radical, or the radical of anorganic acid, as insecticidal, acaricidal, ovicidal and fungicidalagents.

Pluoro-acetyl ureas are prepared advantageously from monofluoro-acetylhalide or monoiluoro-acetic anhydride and mono-substituted ureas byheating the components in an inert solvent, e.g., benzene, toluene,chloro-benzene, if desired under reflux, separating the product, ifnecessary following precipitation with, cg, petroleum ether andrecrystallizing it.

The exothermic reaction of monoiluoro-acetarnide with isocyanates iscarried out by heating the reactants to a temperature in the range of100 to 200 C. In order to avoid possible local overlies-tings it may beadvantageous to carry out the reaction by heating in an inert solvent,e.g., in benzene, toluene, chlorobenzene, dioxane or tetra'hydrofurane.

Instead of the isocyanates there may also be used compounds which underthe above conditions form isocy-anates Carbamic acid chlorides arementioned by way of example.

It is surprising that bromine in sodium hydroxide solution does not acton monofluoro-acetamide analogously to the Hoffman decomposition, but asfollows:

BmNaOH sCmrHCoNH CHgF.CO.NH.C O.NH.CH2.NH.C 0.01121 with formation ofN-monofluoro-acetyl-N'-monofiuoroacetamidomethyl urea, comprisingprobably the addition of one molecule of monoiiuoro-acetamide to theintermediately formed monofluoro-methyl isocyana-te. The urea derivativeso formed is unstable under the reaction condition separateshydrofluoric acid, and adds another molecule of monoiluoro-acetamide.

The reaction of monoiluoro-acetamide with oxalylchloride is suitablycarried out in a molar ratio of about 2:1 in an inert solvent, e.g.,benzene or toluene, by heating under reflux. Probably also in thiscase-{perhaps by splitting oil formylchloridethe correspondingisocyanate is formed to which a second molecule of monofluoro-acetamideadds.

The fluoro-acetyl areas may be used according to the invention in theform of solutions or suspensions for the control of pests. Suitablesolvents among others are alcohols such as methanol, ethanol, propanolor isopropanol, ketones such as acetone, and dimethyl-formamide. On theother hand, the urea derivatives can be also applied in the form ofsolid or liquid preparations, e.g., as wettable powders, dusts, andemulsion concentrates.

As additives to: the formation of solid preparations, there may be usedcolloid protectives and dispersing agents, e.g., cell pitch (sodium orcalcium l-ignine sulfonate), wetting agents, e. g., alkylaryl sulfonate,poly X ethylated alkyl phenols or fatty acid methyltaurides, and inertsubstances, e.g., active silicic acid, talcum, and kaolin. For thepreparation of liquid formulations a non-ionogenic Wet-ting agent, e.g.,an oxyethylated alkylphenol, an oxyethylated alcohol or ester or anoxyethylated carboxylic acid, or an ionogenic wetting agent, e.g., thecalcium salt of an allrylaryl sulfonic acid, or a mixture of bothWetting agents, is added to the active substance in addition to thesolvent or diluent.

As examples of active substanws according to the invention there arementioned:

N-monofiucro-acetyl urea, N,N'-bis-monofiuoro-acetyl urea,N-monolluoro-acetyl-IJ'-methyl urea, N-monofluoro-acetyl-N pentyl urea,N-monofluoro-acetyl-N'-undccyl urea, N-monolluoro-acetyl-N'-octadecylurea, N-monofluoro-acetyl-N lznethyl propyl urea,N-monofluoroacetyl-N-monofiuoro-acetamido methyl urea,N-monofluoro-acetyl-N-fi-chlorethyl urea, N-monofiuoro-B-phenyl ethylurea, N-monolluoro-acetyl-N-benzyl urea, N- monofluoro-acetyl-N'-allylurea, N-monofluoro-acetyl- N-cyclohexyl urea,N-monofluoro-acetyl-N-phenyl urea, N-rnonofiuoro acetyl-N-p-chlorophenylurea, N-monofl-uoro-acetyl-N-p-nitrophenyl urea,N-monofiuoro-acetyi-N-tolyl urea, N-monofluoro-acetyl-N'-p-tertiarybutyl-phenyl urea, and N-monofiuoro-ace-tyl-l\T-p-tolylsuli'onyl-urea.

It is to be noted that the fiuoro-acetyl ureas prepared according to thepresent invention as Well as their formulations can be applied incombination With other insecticides or fertilizers.

The following examples illustrate the invention but they are notintended to limit it thereto:

EXAMPLE 1 N-monofluoro-acelyl urea (a) A benzene solution of 1 mole ofmon-ofiuoro-acetamide and 1 mole of N-carbonyl sultamic acid chlorideare heated weakly and the crystal mass formed is decomposed with Water.After recrystallization from ethanol the yield amounts to about 30% ofthe theoretical yield. Melting point: 210 to 211 C. (decomposition).

Calculated: C, 30.0%; H, 4.17%; N, 23.35%. Found: C, 30.6%; H, 4.5%; N,23.0%.

(b) A benzene solution of 1 mole of monofluoro-acetyl chloride and 1mole of urea is heated under reflux. After the evaporation ofhydrochloric acid, the reaction product is separated and recrystallizedfrom methanol. The yield amounts to about 35 of the theoretical. Meltingpoint: 2 .0 to 211 C. (decomposition).

Calculated: N, 23.35%. Found: N, 23.1%.

3 EXAMPLE 2 A benzene solution of 1 mole of monofluoro-acetamide and 0.5mole of oxalyl chloride is heated under reflux and 4 EXAMELE 7 Thesystemic effects on pests of the active substances identified in Example6 can be proved by surrounding the stems of plants infested withplant-lice (e.g., Vicia faba after cooling, filtration andrecrystallization from water, ztg g ai z i gfg ggfgg fg g g gg iggg g gi z ig gg gg g 32 8 of 40% bandage having been impregnated with 1milliliter of an o C T ii? fi g F 5 N 17 aqueous dilution of 0.1%strength of an agent having the a a e on compositions described inExample 6. The plant-lice oc- EXAMPLE 3 1O curring at the upper parts ofthe plants will perish within N-monofluoro-acetyl-N-methyl urea 3 daysEXAMPLE 8 maerrata:5523;.2 astestrantin A11 esperz' um are estroye Witin ays a ter aving l g" p of tained in a yield of about 30% of thetheoretical yield. sirength of a formulatmn colitammg 25% of N mom' 189to c fiuoro-acetyl-N -phenyl urea, h-monofiuoro-acetyl urea or M mg 3: 29 F d N 20 97 N,N-bis-monofluoro-acetyl urea, 64% of active SlilClC Calmate Gun 0 acid, 10% of cell pitch and 1% of fatty acid methyl- EXAMPLE 4tauride.

The monofluoro-acetyl urea derivatives of the general EXAMPLE 9 f l Whenbean plants that are strongly infested with mites are sprayed with asuspension of 0.2% strength of a forthe characteristics of which aregiven in the fol owin E -g as descnked m f 8, an mlte Stages, even161Ill8 are estroe. table, Were prepared by heating equinmolarquantities of 7 go 7 the isocyanate indicated in column 1 and ofmonofiuoro- EXAMPLE 10 acetamide to temperatures in the range of 100 to150 C. Ticks or medium size Ornithodorus moulaba are de- A 1 IsocyanateR-NCO Yield* Recrystallized Melting a ysls R: point Oaleul. Found 11Pentyl About 50%.. Methanol/water 96-980 14.7% N 14.4% N. Undecyl About65% Methanol Ell-94 10.2% N 10.9% N. Octadecyl About 55%..-- 7.5% N 7.2%N. Z-methylpropyl. About 15.9% N 15.7% N. fl-Oh rethyL. About 30%.--.15.3%N 15.3% N.

en O11 All ii About 40%--.- o 17.5 7311--- 17.5%, N. Cyclohexyl About70%-- {2% ggggggg ggg res-137 13.9% N 13.9% N. Phenyl About 80%..--Ohlorobenzene 159161 g:

p-Ohlorophenyl About 85% 183-184 154% CL. 15.5% C1. p-Nitrophenyl About75% 225227" 17.4% N 17.3% N. p-Tolyl About 70%.." g g 177-179 13.3% N.-.13.3% N. p-Tert.butylphenyl About 65% Methanol 174-175 11.3% N 11.1% N.p-Tolylsulfonyl About o 158-151 11.7% S 10.5% S.

*The yields refer to the pure product.

EXAMPLE 5 stroyed Within 48 hours by a treatment with a 0.4% sus- Whenplants infested with plant-lice, e.g., celery with Dysaulacorthumvincae, are sprayed with a 0.0085% suspension of a preparationcontaining 25% of N-monofluoro-acetyl-N'-phenyl urea, monofiuoro-acetylurea, N,N'-bis-monofiuoro-acetyl-urea or N-monofluoro-acetyl-N'-4-chlorophenyl urea, 64% of active silicic acid, 10% of cell pitchand 1% of fatty acid methyltauride, all plantlice are destroyed.

pension of a wettable powder containing 25% ofN-monofluoro-acetyl-N'-phenyl urea, 74% of active silicic acid, and 1%of fatty acid methyltauride.

EXAMPLE 1 1 When Water infested with Ades larvae and containing usefulfish is mixed with an alcoholic solution of 25 manner that the Watercontains =10 ppm. of the active substance, all Aedes larvae aredestroyed after about 20 minutes, whereas the useful fish remainuninjured.

EXAMPLE 12 Cockroaches of the type Phyllodromia germanica are destroyedwithin a short time by a 0. 6% spray liquor prepared from a Wettablepowder containing 25% of N- monofluoro-acetyl-N'-monofluoro-acetamidomethyl urea, 64% of the active silicic acid, 10% of cell pitch, and 1%of fatty acid methyltauride.

EXAMPLE 13 When cockroaches are placed on a plate previously treatedwith a dust consisting of 10% of N-monofluorostrength ofN-rnonofluoro-acety1-N-phenyl urea in sucha b acety1-N'-tolylsulfonylurea and 90% of talcum at a rate of 6.6 grams/square-meter correspondingto 66 kilograms/ 10,000 square meters the cockroaches are killed.

EXAMPLE 14 EXAMPLE 15 Cockroaches of the type Phylloa'romz'a germanicaare destroyed by a 0. 15% aqueous suspension of a wettable powder whichconsists of 25% of N-monofluoro-acetyl- N'-allyl urea, 64% of activesilicic acid, 1 of cell pitch, and 1% of fatty acid methyltauride.

EXAMPLE 1 6 Ticks of the type Ornithodorus moubata are killed by a 0.3%aqueous suspension of a wettable powder consisting of 25% ofN-monofluoro-acetyl-N-Zmethyl-propyl urea, 64% of active silicic acid,10% of cell pitch, and 1% of fatty acid methyltauride.

EXAMPLE 17 Cockroaches of the type Plzyllodromia germanica are killed byan aqueous suspension ready for spraying and which is prepared from awettable powder consisting of of N-monofluoro-acetylN'-octadecyl urea,63% of active silicic acid, 10% of cell pitch, and 2% of fatty acidmethyltauride.

EXAMPLE 18 Ticks of the type Ornithadorus moubata are killed by a 0.7%aqueous suspension of a wettable powder consisting of 25% ofN,N'-bis-monofluorc-acetyl urea, 64% of active silicic acid, 10% of cellpitch, and 1% of fatty acid methyltauride.

EXAMPLE 19 When bean plants infested with mites (T etranychus urticae)are sprayed with a 0.2% dilution of a preparation which contains 25% ofN-rnonofluoro-acetyl-N-2-methyl propyl urea,N-monofluoro-acetyl-N'-ally1 urea or N- monofluoro-acetyl-N-cyclohexylurea, 64% of active silicic acid, 10% of cell pitch, and 1% of fattyacid methyltauride, all stages of mites including eggs are killed.

6 EXAMPLE 20 When applying ppm. of N,N'-bis-monofluoroacetyl urea orN-monofiuoro-acetyl-'N'-phenyl urea, the outbreak of disease in vinesinfected with Peronospora is entirely prevented.

We claim:

1. A compound of the formula in which R represents a member of the groupconsisting of alkyl of 1 to 18 carbon atoms, allyl, benzyl, phenylethyl,cyclohexyl, chloroethyl, phenyl, chlorophenyl, nitrophenyl, lower alkylphenyl, tolyl sulfonyl, monofluoroacetyl andmonofluoroacetylamidomethyl.

'2. N,N'-bis-rnonotfluoro-acetyl-urea.

N-monofiuoro-acetyl-N'-rnethyl-urea.N-rnonofiuoro-acetyl-N-n-pentyl-urea.N-monofiuoro-acety1-N'-undecyl-urea.N-monofiuoro-acetyl-N-octadecyl-urea.N-monofluoro-acetyl-N'-2-methylpropyl-urea.

. N-monofiuoro-acetyl-N'-B-chloroethyl-urea.N-monofluoro-acetyl-N-;8-phenylethyl-urea.

111. 'N-monofluoro-acetyl-N'-ally1-urea.

1 2. N-monofluoro-acetyl-N-cycloheXyl-urea.

13. N-monofiuoro-acetyl-N-phenylurea.

14. N-monofluoro-acetyl-N-p-chlorophenyl-urca.

15. N-monofiuoro-acetyl-N'-p-nitrophenyl-urea.

16. N-monofluoro-acetyl=N'-p-tolyl-urea.

17. N-monofiuoro-acetyl-N'-p-tert.butylphenyl-urea.

18. N-monofluoro-acetyl-N'-p-tolylsulfonyl-urea.

1'9. N-monofiuoro-acetyl N monofluoro-acetamidomethyl-urea.

sses.

References Cited by the Examiner UNITED STATES PATENTS 2,562,863 7/ 5'1Hoegberg 260-553 2,801,200 7/57 Hackmann 16722 FOREIGN PATENTS 162,8575/55 Australia.

IRVING MARCUS, Primary Examiner. WALTER A. MODANCE, Examiner.

1. A COMPOUND OF THE FORMULA